Cationic monoazo dyestuffs containing a dicarboximido radical



United States Patent Ofiice 3,415,807 Patented Dec. 10, 1968 3,415,807 CATIONIC MONOAZO DYESTUFFS CONTAINING A DICARBOXIMIDO RADICAL John G. Fisher and James M. Straley, Kingsport, Tenm, assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey No Drawing. Filed Oct. 8, 1965, Ser. No. 494,253 7 Claims. (Cl. 260-158) ABSTRACT OF THE DISCLOSURE Quarternary thiazoly1- and henzothiazolyl-azo-indole compounds having a dicar boximidoalkyl group attached to the indole nitrogen atom which are useful as dyes for acrylic and modacrylic textile materials.

This invention relates to novel compounds containing a dicarboximido radical, and more particularly to cationic azo compounds, such as cationic azo dyestutfs, containing a dicarboximido radical.

The azo compounds of the invention have the general formula wherein R=a Z-thiazolyl radical, i.e.,

l s Kl N y i or a Z-benzothiazolyl radical, i.e.,

I wherein 65 R =lower alkyl, e.g. methyl; aryl, e.g. phenyl; R =hydrogen; lower alkyl, e.g. methyl; alkoxy, e.g. methoxy; carboalkoxy, e.g. carbomethoxy; halogen, e.g. chlorine; nitro; cyano and the like;

R =lower alkylene, e.g. CH --CH CH --CH CH Z=a dicarboximido radical, i.e.,

C O o o a wherein B=carbon atoms necessary to complete the ring, such as vinylene, e.g. -CH=CH-; alkylene, e.g.

-CH CH o-phenylene, e.g.

and the like; and A=an anionic material, e.g.

(-1 omsofr, 011F640:

and the like, i.e. an acid anion.

Representative dicarhoximido radicals Z are: succinimido, phthalimido, tetrachloro phthalimido, tetrahydro phthalimido, hexahydro phthalimido, 4-carboxy phthalimido, S-nitro phthalimido, 3-methy1 phthalimido, S-aminophthalimido, glutarimido, bicyclo[2.2.1]-5-heptene-2,3-dicarboximido 1,8-naphthalimido, citraconimido, cycloalkanedicarboximido e.g.

o o 0 H2 hN/C O CO K OOOH:

alkyl succinimido e.gt

oo-cnom C O-CH2 alkenyl succinimido e.g.

O O--CH--CH:CH=CHCH3 campherirnido --N C(GHz):

\G O-- H CH:

The azo compounds of the invention are prepared by coupling the diazonium salts of well known 2 aminothiazoles or Z-aminobenzothiazoles having the formulae with dicarboximido alkyl indole coupling components which have the formula wherein x, y, Z, R R R R and R are the same as defined above. The azo dye thus formed is treated, usually at an elevated temperature, with an alkylating agent such as dimethyl sulfate, methyl-p-toluene sulfonate, methyl iodide, benzyl bromide or the like, either in the presence or aJbsence of a solvent, to yield the cationic dyestuff.

The carboximido alkyl indoles are prepared by reacting an aminoalkylindole with an anhydride, such as succinic anhydride, at an elevated temperature. The aminoalkylindole coupling components are prepared by catalytic re duction of a cyanoalkylindole. The latter compounds may be prepared by reaction of a chloroalkylnitrile with the alkali metal salt of the indole or, in the case of B-cyanoethylindole, by reacting acrylonitrile with the indole.

The following examples will serve to illustrate the preparation of the couplers of the invention and the formation of the dyes from them.

EXAMPLES OF CARBOXIMIDO ALKYL INDOLE COUPLERS Preparation of 1 3-cyanoethyl-2-phenylindole CHaCHnCN Preparation of 1-' -aminopropyl-2-phenylindole An amount of 100 g. of the above product was reduced in an autoclave under hydrogen pressure in 400 ml. of alcohol and 50 g. of anhydrous ammonia. The product was distilled under vacuum yielding 68 g. of l-v-aminopropyl-Z-phenylindole boiling at 1856 C. at 0.8 mm. and has the structure:

Preparation of 1-'y-succinimidopropyl-2-phen lindole An amount of g. of 1-fl-cyanoethyI-Z-phenylindole and 12 g. of succinic anhydride were gradually heated to 160 C. and held at 160-180 for 1.5 hr. The melt was poured into 200 ml. of alcohol and the crystalline product filtered off and dried. The yield was 32.6 g. and the product has the structure:

OOCH:

4 EXAMPLES OF THE DYES Example 1 An amount of 10 ml. of 1-5 acid (1 part propionic: 5 parts acetic) was added to a solution of nitrosyl sulfuric acid prepared from .72 g. of NaNO and 5 ml. of H 1.0 g. of Z-aminothiazole was added keeping the temperature below 5 C., then a second portion of 10 m1. of 1-5 acid was added below 5 C. The diazotization was completed by stirring at 3 to 5 C. for 2 hr. The diazo solution was added to a soltuion of 3.32 g. of l-y-succinimidopropyl-Z-phenylindole in 20 ml. of 1-5 acid cooled in an ice bath. The coupling mixture was buffered by addition of solid NH OAc keeping the temperature below 10 C. After 2 hr. standing with intermittent stirring the dye was precipitated by addition of 800 ml. of water. It was collected on a filter, washed well with water and dried at room temperature. The dye has the structure:

N ll 1.:

SHaN Example 2 COCH:

An amount of 1 g. of the dye of Example 1 was heated in 10 ml. of dimethyl sulfate at -100 C. for 1 hr. After drowning with ether the precipitated quaternary dye was dissolved in water, filtered and reprecipitated by addition of Nal. It dyes acrylic fibers in fast red shades. This dye has the formula:

COCH:

C3HON COCH:

Example 3 Example 4 An amount of 5 g. of a dye prepared as in Example soiom ILN:

CaIIuN In accordance with the method of Examples l-4, a variety of dyes were prepared as illustrated in the fol- CaHsN COCK:

COCH:

Example 13 1 g. of a dye prepared as in Example 11 substituting l-'y-succinimidopropyl-Z-methylindole as the coupler was quaternized by heating in ml. of dimethyl sulfate at 95-400 C. for 1 hr. The red solution was drowned in ether and the sticky solid thus precipitated was dissolved lowing table. The color is that obtained on acrylic fibers. in water, the solution filtered and the dye precipitated as TABLE Examples X Y R; A() R R, R5 B Color 5 (111:; H @CHP Br Q -C2Hr- H C:H4- Bluish-red.

6 CF; H CH; I Q OsH6 H -C|H4- Reddish-orange.

7 H H CH: I Q -CsHu -CO:C:H5 -CzHr- Red.

8 H H CH: I Q --CsHe-- Cl CaH4- Red.

9 CH3 CH: CH: Cl Q CzHa-- H --C|Hr Blulsh-red.

10 H ClHnSOg OH: I Q -C:Hs- H CgH4-- Orange.

Example 11 the iodide by addition of NaI. It dyes acrylic fibers in red An amount of 1.5 g. of 2-aminobenzothiazole was dissolved in 24 ml. of water and 14 ml. of H 80 A solution of nitrosyl sulfuric acid prepared from .72 g. of NaNO and 5 ml. of H 80 was added at 4 to 6 C. After stirring for 2 hr. at this temperature the diazo solution was added to a cooled solution of 1-7-succimido propyl-2-phenylindole in 20 ml. of 1-5 acid. The coupling mixture was buffered with NH OAc and allowed to stand for 2 hr. with intermittent stirring. The dye was isolated by drowning in 1 l. of water, collecting on a filter, washing with water and drying. The dye has the structure:

Example 12 An amount of 1 g. of the dye of Example 11 was dissolved in ml. of dry chlorobenzene. After addition of .75 g. of methyl-ptoluene sulfonate in 10 ml. of dry chlorobenzene the reaction mixture was stirred and heated on the steam bath for 1.5 hr. After cooling, the quaternized dye was filtered, washed with hexane and dried in a vacuum desiccator. It dyes acrylic fibers in slightly bluish-red shades which show good fastness properties. This dye has the structure:

shades. The formula is:

0113 9 l s; l

3 \N/ 00 on,

( /Hg C H: C H2N\ CO C H: Example 14 (3113 6 9 CHaO I N=N l 3 oN I COCHI In accordance with the method of Examples 6-14, a variety of dyes were prepared as illustrated in the following Table. The color is that obtained on acrylic fibers.

A particularly efiicacious group of modacrylic polymers is an acetone soluble mixture of (A) 70-95% by weight of a copolymer of 30-65% by weight of vinylidene TABLE Examples R4 R; A() R R1 Ro B Color None on. 1 Q CsHon -on=cn- Red.

16 None on, 1 Q C Hs- H Red.

01 17 None on. 1 Q -o.m- H 01 Red.

01 F 18 None 011, I Q -cn-cnl-on,- n CHrCH7- Red.

19 eomon. 1 Q -c.Htn CH1-CH:- Blulsh-red.

20 frdi-CHzon, 1 Q -c=n.- H OH;CH Do.

21 ecnioon, 1 Q O;Ho n CHz-CHr- Red-violet.

22 eomson, I Q -oim- H -cH,-orn- Bluish-red.

2s eornso, on, I Q 'C3Hb H -cn,-cn,- Red-organs.

24 e-nmsmon, 1 Q -clHo- H -CH;CH1 Red.

Textile materials dyed by the azo compounds are characterized by containing at least about 35% combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 85-5% of vinyl pyridine units as described in U.S. Patents 2,990,393 (Re. 25,533) and 3,014,008 (Re. 25,539) or modified by 65-5% of vinylpyrrolidone units, for example, as described by U.S. Patent 2,970,783, or modified with 65-5 acrylic ester or acrylamide units as described in U.S. Patents 2,879,253, 2,879,254 and 2,838,470. Similar amounts of the other polymeric modifiers mentioned above are also useful. A preferred group of the copolymers readily dyeable with the azo dyes are the modacrylic polymers such as described in U.S. Patent 2,831,826 composed of a mixture of (A) 70-95% by weight of a copolymer of from to 65% by weight of vinylidene chloride or vinyl chloride and 70- by weight of acrylonitrile, and (B) 30-5% by weight of a second polymer from the group consisting of (1) homopolymers of acrylamidic monomers of the formula wherein R is selected from the group consisting of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) copolymers consisting of at least by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

chloride and 70-35% by weight of acrylonitrile and (B) '30-5% by weight of an acrylamide homopolymer having the above formula wherein R R and R are as described above. Specific polymers of that group contain 70-95% by weight of (A) a copolymer of from 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 30-5% by weight of a lower N-alkylacrylamide polymer such as poly-N-methacrylamide, poly- N isopropylacrylamide and poly N-tertiarylbutylacrylamide.

The following example illustrates one way in which the azo compounds of the invention can be used to dye acrylonitrile polymer textile material. .1 gram of dye is dissolved by warming in 5 cc. of methyl Cellosolve. A 2% aqueous solution of a non-ionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 cc. with warm water. 5 cc. of a 5% aqueous solution of formic acid or acetic acid are added and then 10 grams of fabric made from an acrylic fiber is entered and in the case of Orlon 42 the dyeing is carried out at the boil for one hour. In the case of materials made of Verel acrylic fiber the dyebath temperature should not exceed C. in order to avoid damage to the fiber. The dyed material is then washed well with water and dried.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

9 10 What we claim is: 4. The compound 1. An azo compound having the formula CH3 I a; R-=N I A Ru N=N 185- N/ S I A9 00 l I 00 on, R2 N B CHHiCHICHl-N CO COCH2 wherein: R is a group having the formula wherein A is an anion. X N N 1 J? or R 5. The comggund Y a S \S 1\|I$ wherein X is hydrogen, lower alkyl, phenyl, chlorine, bromine, 6

acetyl, or trifluoromethyl; S I A Y is hydrogen, lower alkyl, acetyl, lower alkylsulfonyl,

or acetamido; T 904m? R is lower alkyl or benzyl; and omcmom-N R is hydrogen, lower alkyl, methoxy, acetyl, acet- CO CH2 amido, chlorine, bromine, thiocyano, methylthio, carbomethoxy, sulfamoyl, N-methylsulfamoyl, N,N- diethylsulfamoyl, methylsulfonyl, or cyano; e n A n an anion. R is lower alkylene; The compound 7 R is lower alkyl or phenyl; OH R; is hydrogen, lower -alkyl, methoxy, carbomethoxy, carboethoxy, chlorine, bromine, nitro, or cyano; B is ethylene, propylene, isopropylene, vinylene, rnethylvinylene, o-phenylene, tetrachloro-o-phenylene, tet- A9 rahydro o-phenylene, nitro-o-phenylene, methyl-o- I phenylene, amino-o-phenylene, bicyclo[2.2.1]-5-hep- N/ 604m tene 2,3-ylene, 1,8-naphthylene, 1,2-cyc1ohexylene, 1,1 cyclohexylenedimethylene, or l-cyclohexylene- I methylene; and (IO-CH: A is an anion. 4O 2. The compound CH3 wherein A in an anion.

I [F 7. The compound CH S N N1 A6 I 3 N III (Jo-0H, LIPN GNgCHaCHr-N r0 s l A oo-om OH;

I]! (JO-OH: CHaCHzCHg-N wherein A rs an amon.

3. The compound COOH2 3H3 wherein A in an anion. N$ References Cited A9 UNITED STATES PATENTS 0O 3,346,552 10/1967 Straley et a1. 260-458 i CHARLES B. PARKER, Primary Examiner. CHaCHgCHz-N D. M. PAPUGA, Assistant Examiner. CO 5 wherein A is an anion.

US. Cl. X.R. 260-32614, 326.15, 319.1, 326, 281, 37; 8-41, 55 

